Surface active materials



Patented Oct. 27, 1942 UNITED STATES 2,299,782 SURFACE ACTIVE MATERIALSCharles F. H. Rochester, N.

Allen and Charles V. Wilson, Y., assignors to Eastman Kodak Company,Rochester, N. Y., a corporation of New Jersey No Drawing. ApplicationFebruary 29, 1940, Se-

i'galgNo. 321,599. In Great Britain March 30,

2 Qiaims. (Cl. 260290) This invention relates to surfaceactiveimaterials and more particularly to cationic surfa-ce activematerials and particularly to surface active materials of the cationicammonium salt type.

During the past several years, a number of Surface active materials havebeen found. These materials may be classified as anionic, cationic, ornon-ionic, depending upon whether or not they are ionizable substances,and if so, whether the anion or the cation is surface active. A numberof these surface active materials have dispersing or wetting propertiesand have come to be known as dispersing and wetting agents.

Some of these known surface active materials (also known as capillaryactive materials, lipophyle materials or materials which possessinterface modifying properties) which are cationic and of the ammoniumsalttype are quite soluble in water, and while possessing high surfaceactivity in most cases, they are frequently difiicult to obtain in apure condition which is desirable for certain purposes, such asincorporation of the surface active materials in photographic emulsions(as described in the copending application of Burt H. Carroll, SerialNo. 321,595, filed of even date herewith), now U. S. Patent 2,271,623,dated February 3, 1942.

We have now found that the known cationic surface active ammonium saltscan be converted into perchlorates. In this form the materials arereadily isolated from reaction mixture and are frequently obtained inthe crystalline state. In the crystalline state, the agents aregenerally white in appearance and have sharply defined melting points.Conversion to the perchlorates is accompanied by a diminution of surfaceactive characteristics.

For the most part, the anions occurring in the known cationic surfaceactive ammonium salts are halides, sulfate, alkylsulfate,toluenesulfonate, nitrate and carboxylic acid anions, e. g. formate andacetate. We have found it advantageous to convert these known salts tothe perchlorates by treating an alcoholic or aqueous solution of theknown salt with a water-soluble perchlorate, e. g. sodium or potassiumperchlorate or perchloric acid. Alcohols which are completely misciblewith water are advantageously employed, e. g. methyl. or ethyl alcohol.

The following examples will serve to illustrate the preparation of ournew cationic surface active ammonium salts. These examples ar notintended to limit our invention. The parts given in the followingexamples are parts by weight.

EXAMPLE 1.N- (n-nonyl) -pyrz'dz'nium perchlorate the air.

647 parts of n-nonyl-p-toluenesulfonate and 175 parts of pyridine weremixed together and heated at to C. for three hours, under reflux. Uponcooling the reaction product, it solidified. 413 parts of this crudeN-(n-nonyD- pyridinium p-toluenesulfonate were dissolved in 750 parts ofwarm methyl alcohol. To the resulting dark solution was added a warmaqueous solution of sodium perchlorate (270 parts in 200 partsof water).Upon chilling the resulting mixture for a short time, the pyridiniumperchlorate separated out. It was filtered off and dried in 312 parts(91% yield) of the pyridinium perchlorate as white crystals melting at79 C. were obtained.

The n -nonyl-p-toleunesulfonate employed in the aboveeggample can beprepared according to the method for preparing lauryl-p-toluenesulfonatedescribed in the Jour. Am. Chem. .Soc. 55, 347 (1933).

EXAMPLE 2.-N-(n-heptylthiomethyl) perchlorate 6 parts n-heptylthiomethylchloride (prepared -pyridinium by treating an equimolecular mixture ofn-heptyl mercaptan and formaldehyde with a molecular equivalent ofhydrogen chloride, at 0 to 10 C.) and 2.7 parts of pyridine were mixedtogether and warmed for 15 minutes on the steam bath. The development ofa slight color and an increase in viscosity of the reaction mixtureindicated the formation of N-(n-heptylthiomethyl) -pyridinium chloride.

v The viscous syrup, thus prepared, was dissolved in 25 parts of methylalcohol at 40 to 50 C. To the warm methyl alcoholic solution were added5 parts of sodium perchlorate, dissolved in 10 parts of water. Onchilling the resulting mixture, 9 parts of N -(n-heptylthiamethyl)-pyridinium perchlorate separated out in the form of fine, white, silkyneedles, melting at 89 C.

In a similar manner, n-heptylthiomethyldimethylbenzylammoniumperchlorate, melting at 167 C. and n-dodecylthiomethyl-pyridiniumperchlorate, melting at 114 to 115 C. were prepared.

EXAMPLE 3.-N -(n heptorymethyl) pyridiniumperchlorate 176 parts ofn-heptoxymethyl chloride (prepared by treating an equimolecular mixtureof n-heptyl alcohol and formaldehyde with a molecular equivalent ofhydrogen chloride at 0 to 10' C.) and 90 parts of pyridine were mixedtogether. A reaction took place immediately, considerable heat beingevolved. The crude N-(n-heptoxymethyD-pyridiniurn chloride thus formedwas cooled and dissolved in 400 parts of warm methyl alcohol. To thewarm methyl alcoholic solution was added a warm aqueous solution ofsodium perchlorate parts dissolved in parts of water). On chilling theresulting mixture, 253 parts of the N-(n-heptoxymethyl) -pyridiniumperchlorate separated out as white crystals, melting at 71 to 73 C.

In a similar manner, the following pyridinium erchlorates were preparedfrom pyridinium hlorides:

M.P., C. T-(n-hexoxymethyll-pyridinium perchlorate 66r-(n-octoxymethyD-pyridinium perchloheated in an open dish on the steambath for about 2 hours to remove ether and methyl alco-' hol. 200 partsof an oil which is essentially n-heptoxymethyldimethylbenzyl ammoniumperchlorate were thus obtained. Upon chilling to C., the oil set to aviscous mass.

In a similar manner, the following ammonium perchlorates were obtained:

'M. P. C.

n-Nony1dimethylbenzylammonium perchlorate 65 nHeptoxymethyldiethylbenzylammonium perchlora e oiln-Nonyldiethylbenzylammonium perchlorate oil p ter-Butylphenoxyethoxyethyldiethylbenzylammonium perchlorate oil EXAMPLE5.-N-carbo-n-nonomymethylpyridinium rate 82 (n-nonoxymethyl) -pyridiniumperchlorate l- (n-decoxymethyl) -pyridinium perchlorate 102 l-(n-undecoxymethyl) -pyridinium p e rchlorate '70 1B-cyclohexylethoxymethyl) -pyridinium perchlorate 68- -'70 1 (Bphenylethoxymethyl) pyridinium perchlorate oilT-citronelloxymethylpyridinium perchlorate oilsT-geranioxymethylpyridinium perchlorate N-cinnamyloxymethylpyridiniumperchlorate N-rhodinoxymethylpyridinium p e r c h l 0- rate oilN-(3,7-dimethyloctanoxymethyl) -pyridinium perchlorate 25N-abietyloxymethylpyridinium p e r c h lo.-

rate 011 N ('y-phenyl-n-propoxymethyl) pyridin ium perchlorate oilN-(fl-n-amyloxyethoxymethyl) -pyridinium perchlorate 8586N-sandaloxymethylpyridinium p e r c h l o-' rate 31-34 The pyridiniumchlorides employed to-prepare the foregoing perchlorates were preparedas illustrated in Example 3 by mixing pyridine with the appropriateoxymethyl chloride. The oxy-. methyl chlorides were always prepared bytreating an equimolecular mixture of the appropriate alcohol (e. g.n-hexylalcohol, fi-cyclohexylethyb alcohol, citronellol, rhodinol,abietyl alcohol -or fi-n-amyloxyethyl with a molecular equivalent ofhydrogen chloride, at 0 to 10 C. In the case of Sandaloxymethylchloride, the alcohol involved is actually a mixture of alcohols, viz.those occurring in Sandalwood oil. Where the perchlorate obtained is anoil at ordinary temperatures, it was purified by extracting impuritiestherefrom with diethyl ether and driving off residual ether by warmingtheoil.

EXAMPLE 4.-n-Heptoxymethyldimethylbenzylammonium perchlorate To 85 partsof dimethylbenzylamine were added 100 parts of n-heptoxymethyl chloride.The mixture became quite hot. It was stirred and allowed to cool to roomtemperature. The thick viscous syrup thus obtained was essentiallyn-heptoxymethyldimethylbenzylammonium chloride.

This viscous syrup was dissolved in 125 parts of warm methyl alcohol andto the warm alcoholic solution was added a warm aqueous solution ofsodium perchlorate (150 parts dissolved in 100 parts of water). An oilseparated at once and some sodium chloride precipitated. Suflicientwater was added to redissolve the sodium chloride. The oily layer wasseparated from the aqueous layer. The oily layer was shaken with diethylether to remove unchanged amine and unchanged n-heptoxymethyl chloride.The oily product was separated from the ether and then alcohol) and.formaldehydeperchlorate 5 parts of n-nonylchloracetate (prepared bytreating chloracetic acid with n-nonyl alcohol) and 2 parts of pyridinewere placed in 25 parts of dry benzene and the solution was heated on asteam bath,.-under reflux, for 18 hours. The solution became very darkand the N-carbo-nnonoxymethylpyridinium chloride failed to crystallizeout upon cooling the solution. Thesolventbenzene was removed bydistillation on the steam bath.

The residue from the aforesaid steam distillation, consistingessentially of crude N-carbo-nnonoxymethylpyridinium chloride, wedissolved in 20 parts of methyl alcohol. To the methyl alcoholicsolution was added 4 parts of sodium perchlorate dissolved in 10 partsof water. Upon chilling the resulting mixture, 2.3 parts of thepyridinium perchlorate, as a yellow flaky salt, separated out. It meltedat 92 C.

In a similar manner, 'y-( -phenylbutyroxwpropylpyridinium perchlorate,melting above 200 C was prepared. The 'y-(v-phenylbutyroxm-'propylpyridinium chloride employed to prepare EXAMPLE6.-N-(p-capro:ruethyl) -pyridini1um perchlorate 1.5 parts ofp-chloroethyl caproate (prepared by the interaction of ca'proyl chlorideand ethylene chlorohydrin) were mixed with 2 parts of pyridine and themixture was heated for 2 hours at to C., under reflux. On cooling thereaction mixture, a viscous mass of crude N-(B- caproxyethyl)-pyridinium chloride was obtained.

This crude pyridinium chloride was dissolved in 15 parts of methylalcohol and to the methyl alcoholic solution were added 5 parts ofsodium perchlorate dissolved in 10 parts of warm water. Upon chillingthe resulting solution, an oil separated. The oily layer was removed andwashed with diethyl ether to remove unchanged reactants. The oil wasthen heated on the steam bath to remove residual ether. The resultingoil was essentially N-(p-caproxyethyl)-pyridinium perchlorate.

EXAMPLE 7.--N- (n-butoxyethoxyethyl) -pyridinium perchlorate 3.1 partsof n-butoxyethoxyethyl chloride (prepared from Butyl Carbitol andphosphorous pentachloride according to'the method of Palomaa andKenetti, Ber. 64, 798, (1931)) and 1.5

parts of pyridine were mixed together and heated, under reflux, for 3hours at 125 to 135 C. Upon cooling, a viscous mass resulted which wasessentially N- (n-butoxyethoxyethyl) -pyridinium chloride.

The aforesaid pyridinium chloride was dissolved in 15 parts of warmmethyl alcohol and to the warm alcoholic solution, 2.5 parts of sodiumperchlorate, dissolved in 10 parts of warm water, were added. Afterchilling to C. for several hours, an oily layer separated. The oilylayer was removed from the aqueous layer and washed with diethyl etherto remove unchanged reactants. The oil was then heated on a steam bathto remove residual ether. The 011 thus obtained was essentiallyN-(n-butoxyethoxyethyhpyridinium perchlorate.

EXAMPLE 8.-N

ethyl) p ter butylphenomyethoxy -p 1 rz'clinium perchlorate parts ofmethyl alcohol and to the alcoholic solu tion were added 17 parts ofsodium perchlorate dissolved in 20 parts of warm water. Upon cooling theresulting mixture, 23 parts of the pyridinium perchlorate separated outas a white flaky crystalline material, melting at 64 to 69 C.

In a similar manner, the following related perchlorates were obtained:

3 2 4 -oo11icHiocHzoH, N c1o.

M. P. C. 4-methyl 63-64 4-ethyl oil 4-isopropyl 133 4-ter-amyl oil4-cyclohexyl 105 2,4-dimethyl oil 3-methyl-6-isopropyl 78-802-methyl-5-lsopropyl 87-89 2-phenyl oil 4-phenyl 134 2-benzyl 135 4-benzyl 67 2-hydroxymethyl 146-147 4-chloro 79 2,4-dichloro 88-904-bromo 61-63 2-iodo 75 4,4-chlorophenyl 79-812-isopropyl-5-methyl-4chloro 88 4-methoxy 62-64 4 -aceto 98 4-propio 694-n-butyro 61-63 4-a1lyl-2-methoxy oil Z-carboxy 124-126 4-phenylazo105-107 perchlorate dissolved EXAMPLE 9.N (pJorrhylphenoxyethoryethyl)pyridinium perchlorate 2.5 parts of p-formalphenoxyethoxyethyl chloride(prepared by reacting'one molecular proportion of p-hydroxybenzaidehydewith four molecular proportions of p,fi-dichlordiethyl ether at 160 to180 C. for 10w 15 hours, in the presence of solid sodium hydroxide) and1 part of pyridine were mixed together and heated, under reflux. on anoil bath for 3 hours at to C. Upon cooling, the reaction mixture set toa viscous gum.

This gummy product was dissolved in 10 parts of warm methyl alcohol andto the methyl alcoholic solution were added 2 parts of sodium in 6 partsof water. Upon chilling the resulting mixture to 0 C. for several hours,2.3 parts of the pyridinium perchlorate separated out melting at 105 C.

In a similar manner, the following perchlorates were obtained:

a 2 4 -ocmcmocmcm NZc1o.

M. P. C. 3-formyl 104-106 2-methyl-4-formyl-5-isopropyl 1062-isopropyl-4-formyl-5-methyl 97 2-methoxy-4-formyl 1532-ter-amyl-4-formyl oil 2-formyl-4-chloro 88-90 2-formyl-4-bromo 56EXAMPLE 10.N p naphthoxyethoxyethyl pyridinium perchlorate -ing mixturewas allowed to stand in an ice chest for 5 hours, when an oil separatedwhich quickly soldified upon stirring. The solid pyridinium perchloratewas filtered off and washed with diethyl ether. It melted at 78 to 81 C.

In a similar manner, N-(a-naphthoxyethoxyethyl)-pyridinium perchlorateand 2(3) -phenanthroxyethoxyethyl pyridinium perchlorate were obtained.Each was obtained as an oil.

EXAMPLE 11.N-(p-methylphenozypropowypropyl) -pyrz'dinium perchlorate 6.5parts of p-methylphenoxypropoxypropyl chloride (prepared by reacting onemolecular proportion of p-cresol with four molecular proportions of'm"-dichloro-di-n-propyl ether at to 180 C. for 10 to 15 hours, in thepresence of solid sodium hydroxide) and 2.5 parts of pyridine were mixedand heated, under reflux, at 125 to 135 C. for 3 hours. Upon cooling,the reaction product was taken up in 15 to 20 parts of methyl alcohol.To this solution, were added 6 parts of sodium perchlorate dissolved in12 parts of water. The pyridinium perchlorate separated as an oil ichsolidified after chilling at C. for several The oily product was washedwith diethyl ether us. The pyridinium perchlorate was recrystalanddissolved in 30 parts of hot methyl alcohol. ad from ethyl alcohol and'7 parts of a white To this hot methyl alcoholic solution, 15 parts of'stalline salt, melting at 64 to 65 C., were sodium perchlorate in 15parts of warm water was tained. added. On cooling the resultingsolution, 13.5 [n a similar manner, N-(p-phenylphenoxyproparts of thecrude perchlorate melting at 8286 xypropyl) -pyridinium perchlorate,melting at separated. When the salt was recrystallized from J C., andN.-(ter-butylphenoxypropoxypropyl)- methyl alcohol, the purifiedperchlorate melted ridinium perchlorate,a.n oil, were obtained. at98-100 C. The salt has the following for- :AMPLEl2.-N-(p-cresylthioethoxycthyl)-pyridinium perchlorate 6.3 parts ofp-cresylthioethoxyethyl chloride 1 repared by reacting one moleculeproportion of thiocresol with four molecular proportions of3'-dichl0rodiethyl ether at 160 to 180 C. for

I to 15 hours, in the presence of solid sodium EXAMPLE 16.-N -(whydroxydecyD- pyridinium zdroxide) and 3 parts of pyridine were mixedperchlorate gether and heated at 125 to 135 C. for 3 )lllS, underreflux. The reaction product was 5 g i of decamethylene chlomhydrm and20 s of pyridine were mixed together and fggg g g gi 1 g l fl ggi g; ag:the mixture was heated, under reflux, in an oil lded 6 parts of sodiumperchlorate, dissolved in bath 3 at a temperature Upon cooling themixture it set to a white 3 parts of water. The pyrldlnlum perchlorateeparated as an oil which solidified upon chilling cake was 1155mm )rseveral days at 0 C. The crude material was f fnethyl alcOhOl- 0 theresulting soluacrystamzed from methyl alcohol and 5 of a tlon, dlethylether was added until aploudmess ,hite crystalline Salt melting at to460 developed. Upon chllllng the resulting cloudy we obtained solutionto 0 C. for 2 hours, 10 parts of the pyridinium chloride separated out.

lXAMPI-E ll ll -Py 2 parts of the pyridinium chloride we e disdiniumperchlorate solved in 10 parts of methyl alcohol and to the resultingsolution were added 2 parts of sodium perchlorate dissolvedin 8 parts ofwarm water. Upon chilling the resulting solution to 0 C., 1.5

4.5 parts of w-phenyltetraoxyethyl chloride prepared by reacting onemolecular proportion 35 finfiiffifilenlliyid etfifffi it it tt it 2.Paris of W i Perchlorate Separated or 10 to 15 hours, in the presence ofsolid sodium out as wmte nd It melted at 51 to 52 lydroxide) and 1.8parts of pyridine were mixed EXAMPLE 17.-N-methyl-n-(n-nonyl)-pyridinium logether and heated, under reflux, at 125 to 135 perchlorate3. for three hours. The reaction mixture was :ooled and taken up in 20parts of methyl alcohol. To the resulting methyl alcoholic solution, 5parts of sodium perchlorate, dissolved in 10 parts of water, were added.The pyridinium perchlorate separated as an oil whichdid not solidifyeven upon several weeks chilling at 0 C. The oil was washed severaltimes with diethyl ether and then heated on a steam bath to removetraces of ether.

The oil still failed to solidify upon prolonged chilling at 50 (n nonyl)pyridlmum-p-toluenesulfonate separated out. It was collected on a filterand Exmm: 14-N. '-deca y e y washed with cold acetone and dried in theair. pip d n um p r h ra 220 parts of faintly yellow crystals, meltingat 134 C. were obtained. 5 parts of decamethylene bromide and 3.5 partsof N-methylpiperidine were mixed together and 55 parts of 'pyndlmum'heated for a few minutes in an on bath at p-toluenesulfonate weredissolved in 32 parts of A vigorous reaction ensued and the mixturebewarm methyl alcohol and to the'resultmg Solucames1id tion were added32 parts of sodium perchlorate, The solid product was dissolved in 20parts of dissolved in 32 parts of water Upon chilling the warm methylalcohol and to the warm alcoholic resulting mixture to 23 Parts thesolution were added 5 parts of sodium perchloratemethyl'a'mmmyl)Pyridmium Perchlorate dissolved in 10 parts of warmwater. Upon chillmated It was filtered \15ing 9- chilled ing theresulting mixture at 0 C. for several tunnel because of its low meltmgPomthours, 3 parts of the piperidinium perchlorate In a Similar manner,r' separated out as white crystals. The crystalspyridinium-P-t0111ene5111f011ate, melting at 88 melted at 186 to 190 C.C., N-methyl-a(n-octyl) -pyridinium-p-toluenesulfonate, melting at 116to 118 C., N-methylm 15' M'n'nonyl'z'phenylpynmldazolmm a. (n decyl)pyridinium p-toluenesulfonate,

perchlorate melting at 99 C., N-methyl-d-(n-undecyh- Five andseven-tenths parts of Z-phenylpyrimipyr nium-p-t0luenesulfonate, m ingat to dazole and 9 parts of n-nonyl p-toluenesulfonate and N-thyl-v-n0nylpyridinium-p-to1- were heated for 3 hours at Mil- C. andcooled. u ate. melting at to 162 C. can be hN-n-nonyI-Z-phenylpyrimidazolium 4 1 prepared and converted to thecorresponding enesultonte separated as an oil. 75 p rates.

142 parts of d-(n-nonyl) -pyridine and 142 parts (10% excess ofmethyl-p-toluenesulfonate were mixed well and allowed to stand at roomtemperature. An exothermic reaction took place,

45 the temperature rose to 125 C, and the reaction mass finallysolidified. The solidified mass was dissolved 700 parts of a warmmixture of 6 parts of acetone to 1 part of methyl alcohol. Upon coolingthe resulting solution, N-methyl-a- EXAMPLE 18.-N heptcrymethyl a-(n-nonyl) pyridinium perchlorate 2.2 parts of (n-nonyl) -pyridine and1.7 parts of n-heptoxymethyl chloride were mixed togeth'er. Heat wasevolved and a gummy product resulted. The gummy product was dissolved in10 parts of warm methyl alcohol and to the resulting solution were added3 parts of sodium perchlorate dissolved in 10 parts of warm water. Anoil separates out immediately. The oil was separated from the aqueousalcoholic layer and then dissolved in methyl alcohol. The methyl alcoholsolution was treated with water until a faint cloudiness developed. Thesolution was then chilled to C. N-heptoxymethyl-a-(nnonylJ-pyridiniumperchlorate separated out as white crystals, melting at 61 C.

EXAMPLE pyridinium perchlorate 6.7 parts of n-heptyl picolinate and 5.6parts of methyl-p-toiuenesulfonate were mixed together and heated for 3hours at 125 to 135 0., under reflux. The reaction mixture solidifiedupon cooling and was recrystallized from a small volume of acetone. Therecrystallized product was washed with diethyl ether and allowed to dry.In this manner, 6.5 parts of the pyridiniump-toluenesulfonate wereobtained as bufl crystals, melting at 108 C. A portion was converted tothe perchlorate in the manner illustrated in the above example.

Similarly, the following pyridinium p-toluenesulfonates were preparedand converted to the corresponding pyridinium perchlorates.

M. P. C. N methyl a- (carbo-n-octoxy) pyridinium-p-toluenesulfonate 110N methyl -p-carbo-n-heptoxy) -pyridinium-p-toluenesulfonate 85 N methyl-p-(carbo-n-o'ctoxy) -pyridinium-p-toluenesulfonate 88-89 N nonylp-(carbo-n-octoxy) -pyridinium-p-toluenesulfonate 100 EXAMPLE20.--N-methyl-a-tridecylpyridinium perchlorate 2.6 parts ofa-(n-tridecyl) -pyridine and 1.4 parth of methyl iodide were mixedtogether and allowed to stand overnight at room'temperature. Theresulting solid reaction product was dissolved in 10 parts of warmmethyl alcohol. To this solution were added 3 parts of sodiumperchlorate dissolved in parts of warm water. The resulting mixture wasallowed to stand in an icebox for several hours when white crystalsofthe pyridinium perchlorate separated out. These crystals (2.1 parts)melted at 20 C. and are advantageously filtered off using a chilledfunnel.

N (n -heptoxymethyl)--trideeyl-pyridinium perchlorate, melting at 23 C.was similarly prepared from N-(n-heptoxymethyl)-a-tridecylpyridiniump-toluenesulfonate which was obtained as a gum by the interaction of-(n-tridecyD-pyridine with methyl-p-toluenesulfonate.

EXAMPLE 21.0ctyl dimethyl sulfonz'um perchlorate arate. This oil wasthrown out by the addition 19.-N-methyl-a- (carbo-n-heptomy) EXAMPLE22.n-Decyl-1-phenyZ-3,5-dimethylpyrazolium perchlorate A mixture of 2.7parts of n-decyl iodide and 1.7 parts of 1-phenyl-3,5-dimethylpyrazolewas heated for 3 hours at 120-150 C. The reaction product was dissolvedin 15 parts of methyl a1- cohol and treated with 3 parts of sodiumperchlorate in 10 parts of water. On chilling for several hours an oilseparated. It was removed from the aqueous alcoholic layer and washedwith ether to remove any unchanged n-decyl iodide or pyrazole, and thenwarmed on the steam bath for a few minutes to remove volatile solvents.There was thus obtained 4 parts of a crude oily product which isessentially n-decyl- 1-phenyl-3,5-dimethylpyrazolium perchlorate.

EXAMPLE 23.Tetramethylene-bis-1-phenyl 3,5 dz'methylpyrazoliumperchlorate A mixture of 2.2 parts of tetramethylene bromide and 3.4parts of 1-phenyl-3,5-dimethylpyrazole was heated for 3 hours at-120-150C. The product, which was essentially tetramethylene-bis-l-phenyl 3, 5dimethylpyrazolium bromide, fails to solidify on cooling. It wasdissolved in 15 parts of methyl alcohol and treated with a warm solutionof 3 parts of sodium perchlorate in 10 parts of water. On chilling forseveral hours, the tetramethylene-bis-1-phenyl-3,5-dimethylpyrazoliumperchlorate separated as an oil. It was removed from thealcoholic-aqueous layer and dissolved in 15 parts of warm acetone. Onchilling this solution, 1.5 parts oftetramethylene-bis-1-phenyl-3,5-dimethylpyrazolium perchlorate separatedas a white salt melting at 216-218 C.

The cationic surface active quaternary ammonium perchlorates having acation which contains a chain of at least eight members are especiallyuseful substances for incorporation in photographic emulsions.Advantageously, such members are from the group consisting of carbon,oxygen and sulfur atoms. One or more aromatic rings, such as a benzenering for example, can take the place of one or more of the eight or moreatoms. Thus, a benzene ring can take the place of one atom, while anaphthalene ring (two benzene rings fused together) can take the placeof two atoms. The atoms attached to the.eight or more atoms in the chain(where valence permits) can be hydrogen, oxygen, sulfur, carbon orhalogen for example. Any aromatic ring system in the chain can carrysimple substituents. The organic group containing a chain of eight ormore atoms can be directly attached to the quaternary ammonium nitrogenatom or indirectly thereto by means of a group of atoms. Cationicsurface active quaternary ammonium perchlorates having an ammoniumcation containing a lipophylic organic group which contains a chain offrom nine to twelve members selected from the group consisting of carbonatoms, oxygen atoms, sulfur atoms and aromatic ring systems areespecially useful. More specifically, the N-alkoxymethylpyridiniumperchlorates, the alkoxymethyldimethylbenzylammonium perchlorates andalkoxymethyldiethylbenzylammonium perchlorates, in which the alkoxygroup is one of the formula CnH2n+1O wherein n represents a positiveinteger of from 6 to 10 i that we have provided are especially useful,as are the quaternary pyridinium salts characterized by having attachedto one of the carbon atoms of the pyridine nucleus an organic groupcontaining a chain of at least eight atoms.

It is, therefore, apparent from the foregoing perchlorate derivatives ofa variety of surface active materials, of which the ammonium type areprepared. Hence, we do not wish to be restricted in our invention,excepting insofar as is necessitated by the prior art and the spirit ofthe appended claims.

What we claim as our invention and desire to be secured by LettersPatent of the United States is:

. CERTIFICATE OF CORRECTION;

Patent 2,299,782.

CHARLES F. H. ALLEN, ET AL.

1. A cationic surface active quaternary ammonium perchlorate of thefoiiowing general formula:

wherein n represents a positive integer of at least 8.

CHARLES F. H. ALLEN. CHARLES V. WILSON.

October 27, ,19lr2.

It is hereby certified that error appears in the printed" specificationof the above numberedpatent requiring correction as'follows': Page 1;,first column, line 114., for "molecule" nonyl" read -N-n-nony1--; withthis correction therein the case in the Patent 0ffice.

(Seal) read --mo1ecu1ar--;

line 68-, for "ll-nand that the said Letters Patent should be read thatthe samemay conform to the record of fdanuary, A. D. 1911.5.

Henry Van- Arsdale I CERTiFICATE OF coRREcrmm; Patent 2,299,782. October2'], ,19u2.

-' CHARLES F. H. ALLEN, ET AL.

printed specification It is hereby certified that error appears in the'follows': Pagehi, firet of the above numberedpatent requiringcorrection a; column, line 111., for "molecule" nonyl' read--N-n-nonyl--; and that the said Letters Patent should be read with thiscorrection therei the case in the Patent 0ffice.

Signed and sealed this 5th day of January, A. D. 1911.5.

Henry Van Araqele (Seal) Acting Commhissioner of Peten'ta read--mo1ecular-; line 68', f r 'H-nn that the Same may conform to therecord of

